Rendering polyvinyl alcohol fibers containing structure chlorine-fast



United States Patent Ofiiice 3,116,163 RENDERENG POLYVHNYL ALCGHOLFIBERS C(JN- EARNING STRUCTURE CiEilLORllNE-FAST Cari-Ludwig Nottebohmand Robert Schahert, Weinheim der llergstrasse, and WilhelmBiichsenstein, Schriesheim an der Eergstrasse, Germany, assignors toFirma Carl Freudenberg, Kommanditgesellschaft auf Alrtien, Weinheim ander Eergstrasse, Germany No Drawing. Filed Nov. 23, 1959, Ser. No.854,616 Claims priority, application Germany Nov. 28, 1958 8 Qiaims.(ill. 117-140) This invention relates to a method of making chlorinefastsheet structures containing polyvinyl-alcohol fibers.

lany methods for the production of non-woven sheet structures fromfibers are known and are in technical use. It is essential thereby thatthe single fibers adhere sufilciently to one another, which can bebrought about by diiierent methods. One of them consists in the use ofswellable fibers on the basis or" e.g. polyvinyl alcohol per se or incombination with other common non-swellable fibers.

The sheet structures made in this way are not, however, resistant toboiling and chlorine-releasing bleaching agents since the polyvinylalcohol fibers dissolve in hot water.

it has now surprisingly been found that polyvinyl alcohol containingstructures can be made resistant to washing, boiling andchlorine-releasing bleaching agents by after-impregnating non wovensheet material containing polyvinyl alcohol fibersthe former being madeaccording to any of the known methods-with a mixture of an aminopiastand a polymer containing active radicals, such as CN, COOH or NHSuitable aminoplasts are cg. di-methylol-thio-urea,dirnethylol-dihydroxy-ethylene-urea and trimethylolmelamine. Suitable-CN, -COOH or Nl-l containing polymers are methacrylic acid, acrylicacid, arcylonitrile, acryloamide and copolymers thereof.

When carrying out the present invention under the conditions ofpractice, the above named components are dissolved in a solvent such aswater or alcohol. The solvent should be present in abundance, sinceconcentrated solutions would change the character of the material to ibe treated. It has been found that 15% solutions of the above mentionedcompositions cause the desired effect Without impairing the appearance,hand, softness etc. of the starting fiber batt. The sheet materialcontaining polyvinly alcohol fibers is then impregnated with saidsolution as described in the following examples.

Example 1 A fiber batt weighing 4-0 grams per square meter consisting ofPercent Viscous rayon 90 Watersoluble polyvinyl alcohol fibers 10 isimpregnated in a padding mangle with water until a wet pick up of 200percent is reached, then dried in a felt calender and therebystabilized.

This stabilized fibrous sheet material is then impregnated in a paddingmangle with a solution consisting of Percent Water 97.9 Ammoniumoxalate(catalyst) 0.1

The impregnated sheet material is then squeezed off 3,llh,lh3 PatentedDec. 31, 1%53 pregnated with water in the same way as in Example 1,prestabilized in a felt-calender and then impregnated with a solutionconsisting of Percent Water 96.5 Trimetliylol-mclamine 1.5

Copolymer which consists of 50 parts by weight of methacrylic acidbutylic ester, 15 parts by Weight of methacrylic acid methylester and 35parts by Weight of methacrylic acid (commercially available as Plextol)The further steps are the same as in Example 1.

Example 3 A fiber batt made and prestabilized as described in Example 1is impregnated with a solution consisting of Percent Methyl alcohol 97.9Zinc chloride (catalyst) 0.1 Dimethylol-urea 1.0 Acrylic acid 1.0

The further steps are the same as in Example 1. The resulting non-wovenfabric is not so soft as that of the preceding examples where theacrylic acid has been replaced by Perbunan or Plextol.

Example 4 A fiber batt made and prestabilized as described in Example 1is impregnated with a solution consisting of 98.0 percent water 1.0percent dimcthylol-dihydroxy-ethylene-urea 1.0 percent of a copolymerwhich consists of 70 percent methacrylic acid butylester, 20 percentacrylamide and 10 percent methacrylic acid methylester.

The acryloamide is partially methylated. (The copolymer is being sold asAcronal.)

The further steps are the same as in Example 1.

Example 5 A fiber batt made and prestabilized as described in Example 1is impregnated with a solution consisting of 95.7 percent water 0.3percent aluminum chloride 2.0 percent of a copolymer consisting of equalparts of methacryli-c butylester and acrylonitrile.

2.0 percent trimethylolmelamine The further steps are the same as inExample 1.

What We claim is:

1. A process for rendering non-woven fabric containing water solublepolyvinyl alcohol fibers resistant to the action of hot water andchlorine-releasing agents, which comprises impregnating such non-wovenfabric with a 1 to 5% solution of substantially equal amounts of amember selected from the group consisting of dimethylolurea,trimethylol-melamine, and dimethylol-dihydroxyethylene urea and of amember selected from the group consisting of: copolymers ofacrylonitrile, methacrylic acid, and butadiene, copolymers ofmcthacrylic acid butylic ester, methacrylic acid methylester, andmethacrylic acid, copolymers of methacrylic acid butyl ester,acrylamide, and methacrylic acid methyl ester, copolymers of methacrylicbutyl ester and acrylonitrile and polymers of acrylic acid for a wetpick-up of about 100%, and thereafter subjecting the impregnated fabricto temperatures of about 150 C. whereby the polyvinyl alcohol fibers insaid non-woven fabric are modified and said fabric rendered resistant tothe action of hot Water and chlorine-releasing agents.

2. Process according to claim 1, wherein the solution used in saidimpregnating contains a catalyst.

3. A process for rendering non-Woven fabrics containing water solublepolyvinyl alcohol fibers resistant to the action of hot Water andchl0rine-releasing agents, which comprises impregnating said non-wovenfabric with a 15% solution composed of 97.9% Water,

0.1% ammoniumoxalate, as catalyst,

1.0% of a copolymer consisting of 30 parts by weight of acrylonitrile,15 parts by weight of methacrylic acid, and 55 parts by Weight ofbutadiene,

1.0% dimethylol-urea as aminoplast.

4. A process for rendering non-woven fabrics containing water solublepolyvinyl alcohol fibers resistant to the action of hot water andchlorine-releasing agents, which comprises impregnating said non-wovenfabric with a 15% solution composed of 96.5% water,

1.5 trimethylol-melamine,

2.0% of a copolymer consisting of 50 parts by Way of methacrylic acidbutylic ester, 15 parts by weight of methacrylic acid methylester, and35 parts by weight of methacrylic acid.

5. A process for rendering non-woven fabrics containing water solublepolyvinyl alcohol fibers resistant to the action of hot water andchlorine-releasing agents, which comprises impregnating said non-wovenfabric with a 15% solution composed of 97.9% methyl alcohol,

0.1% zinc chloride, as catalyst, 1.0% dimethylol-urea, and 1.0% acrylicacid.

6. A process for rendering non-woven fabrics containing water solublepolyvinyl alcohol fibers resistant to the action of hot Water andchlorine-releasing agents, which comprises impregnating said non-wovenfabric with a 15% solution composed of 98% water,

1% dimethylol-dihydroxy-ethylene-urea,

1% of a copolymer consisting of methacrylic acid butylester, 20%acryloamide, and 10% methacrylic acid methylester.

7. A process for rendering non-woven fabrics containing water solublepolyvinyl alcohol fibers resistant to the action of hot water andchlorine-releasing agents, which comprises impregnating said non-Wovenfabric with a 1-5% solution composed of 97.5% water,

0.3% aluminum chloride,

2.0% of a copolymer consisting of equal parts of methacrylic butylesterand acrylonitrile,

2.0% trimethylol-melamine.

8. A washable, high-temperature, chlorine-resistant, non-Woven fabric,comprising a fabric containing Watersoluble polyvinyl alcohol fiberswhich has been impregnated with a 1 to 5% solution of substantiallyequal amounts of a member selected from the group consisting fdimethylol-urea, trimethylol-melamine, and dimethylol dihydroxy ethyleneurea, and a member selected from the group consisting of polymers ofacrylic acid, copolymers of acrylonitrile, methacrylic acid, andbutadiene, copolymers of methacrylic acid butylic ester, methacrylicacid methylester, and methacrylic acid, copolymers of methacrylic acidbutyl ester, acryiamide, and methacrylic acid methylester, andcopolymers of methacrylic butyl ester, and acrylonitrile for a wetpick-up of about 100%, and thereafter subjected to a temperature ofabout C. whereby said polyvinyl alcohol fibers in said non-woven fabricare modified and said fabric rendered resistant to the action of hotwater and chlorine-releasing agents.

References Cited in the file of this patent UNITED STATES PATENTS2,433,000 Manning Dec. 23, 1947 2,497,117 Dreyfus Feb. 14, 195012,719,806 Nottebohm Oct. 4, 1955 2,864,093 Sumner et al Dec. 16, 19582,962,762 Hartmann et al Dec. 6, 1960 2,973,284 Semegen Feb. 28, 1961UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3, 116163 December 31 1.963

Carl-Ludwig Nottebohm et ala It is hereby certified that error appearsin the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 4 line 14 for 915% read 95 7% 0 Signed and sealed this 19th dayof May" 1964;

(SEAL) Attest:

ERNEST W3 SWIDER EDWARD L BRENNER Attesting Officer Commissioner ofPatents

1. A PROCESS FOR RENDERING NON-WOVEN FABRIC CONTAINING WATER SOLUBLEPOLYVINYL ALCOHOL FIBERS RESISTANT TO THE ACTION OF HOT WATER ANDCHLORINE-RELEASING AGENTS, WHICH COMPRISES IMPREGNATING SUCH NON-WOVENFABRIC WITH A 1 TO 5% SOLUTION OF SUBSTANTIALLY EQUAL AMOUNTS OF AMEMBER SELECTED FROM THE GROP CONSISTING OF DIMETHYLOLUREA,TRIMETHYLOL-MELAMINE, AND DIMETHYLOL-DIHYDROXYETHYLENE UREA AND OF AMEMBER SELECTED FROM THE GROUP CONSISTING OF: COPOLYMERS OFACRYLONITRILE, METHACRYLIC ACID, AND BUTADIENE, COPOLYMERS OFMETHACRYLIC ACID BUTYLIC ESTER,METHACRYLIC ACID METHYLESTER, ANDMETHACRYLIC ACID,COPOLYMERS OF METHACRYLIC ACID BUTYL, ESTER ACRYLAMIDE,AND METHACRYLIC ACID METHYL ESTER, COPOLYMERS OF METHACRYLIC BUTYL ESTERAND ACRYLONITRILE AND POLYMERS OF ACRYLIC ACID FOR A WET PICK-UP OFABOUT 100%, AND THEREAFTER SUBJECTING THE IMPREGNATED FABRIC TOTEMPERATURES OF ABOUT 150*C. WHEREBY THGE POLYVINYL ALCOHOL FIBERS INSAID NON-WWOVEN FABRIC ARE MODIFIED AND SAID FABRIC RENDERED RESISTANTTO THE ACION OF HOT WATER AND CHLORINE-RELEASING AGENTS.